EP0990515B1 - Film comprenant une couche centrale en polyoléfine et deux couches externes en alliage polyamide/polyoléfine - Google Patents
Film comprenant une couche centrale en polyoléfine et deux couches externes en alliage polyamide/polyoléfine Download PDFInfo
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- EP0990515B1 EP0990515B1 EP99402330A EP99402330A EP0990515B1 EP 0990515 B1 EP0990515 B1 EP 0990515B1 EP 99402330 A EP99402330 A EP 99402330A EP 99402330 A EP99402330 A EP 99402330A EP 0990515 B1 EP0990515 B1 EP 0990515B1
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- polyolefin
- polyamide
- alloy
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- film
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/10—Polypropylene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2377/00—Polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/08—Cars
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/12—Ships
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Definitions
- the present invention relates to a new film comprising a central polyolefin layer and two outer layers of a polyamide / polyolefin alloy having a surface tension little different from that of the polyolefin of the alloy.
- the SMC is used in parts manufacturing transformed as well in the automotive fields (bumpers, tailgates ...) than those of the water sports (hulls of boats) or electronics (housings).
- the SMC is generally composed of a crosslinkable polymer resin, in unsaturated polyester, reinforcement such as fiberglass, as well as various other additives in small amounts.
- the SMC is usually prepared by depositing fibers on a layer of unsaturated polyester resin, itself supported on a moving film, usually composed of polyethylene or polyamide. Another film of the same nature is then deposited over the resin / charge system of reinforcement to form a sandwich composite mass between two films. The sandwich then goes through a series of kneading and compaction rollers and is generally rolled up as large rolls. It is then stored before further processing.
- polyester resin reticle partially, causing an increase in viscosity of the SMC, until reaching a consistency that makes it suitable molding.
- SMC users in general molders, cut a piece of suitable dimensions to from the roll, peel off the backing film and place the SMC in a heated mold for the simultaneous transformation and complete cooking. So, composite SMC sandwich masses find a easy application in molding procedures by compression.
- the first relates to permeability styrene film peelable. It is necessary that this film peelable has a very low styrene permeability so to avoid the loss of styrene monomer which plays the role of reactive diluent in SMC. This loss of styrene monomer is also detrimental to the health of individuals during manufacturing operations of the MSC and its storage.
- the second property concerns the facility peel this film on the polyester structure, so that there is no residual film on the structure and to avoid the risk of tearing of this film during manufacturing and processing operations of MSC.
- the moisture uptake and the water permeability of these peelable films must be very weak so that the quality of the polyester resin, very sensitive to water, does not not be altered during the manufacturing operations of the SMC, polyester storage or processing SMC.
- EP-A-0506515 discloses films based on an alloy polyamide / polyolefin, wherein the compatibilizing agent is a functionalized polyolefin (eg, maleate), optionally grafted with a polyamide oligomer low molecular weight. These films are used to SMC (Sheet Molding Compound); they present a tension surface area of about 32 mN / m. However, some thickness is necessary to achieve good mechanical properties, which implies a fairly high cost for the final film.
- SMC Sheet Molding Compound
- EP-A-0786319 discloses useful films for SMC and made of a layer of polyamide / polyolefin alloy disposed between two layers of polyolefin.
- Layer polyamide and polyolefin alloy core is sufficient for styrene impermeability and the layers outer polyolefin are suitable for the coat with the SMC polyester.
- the first solution is not desirable because it implies an extrusion of a five-layer film, which is difficult.
- the second solution increases the voltage of surface of each polyolefin film, and therefore the film final is no longer appropriate for MSC. Moreover, he is not possible to make the core layer alloy sticky by adding a polyolefin graft, because it would then be found at the polyamide / polyolefin interface at the level of the nodules.
- the film consists of a polyolefin core layer between two outer layers polyamide / polyolefin alloy.
- the polyolefin of layer (i) comprises a functionalized polyolefin.
- the polyolefin of the layer (i) comprises a homo- or co-polymer of ethylene or propylene.
- the polyolefin of the layer (i) is a mixture of a non-functionalized polyolefin and a functionalized polyolefin, said functionalized polyolefin representing up to 40% by weight of the mixture.
- the polyolefin functionalized is a mixture PE / EPR grafted anhydride maleic.
- the alloy polyamide / polyolefin is in co-continuous phases.
- the alloy polyamide / polyolefin comprises a compatibilizing agent.
- the alloy polyamide / polyolefin is a PA6 / PP / Agent alloy compatibilizer.
- the compatibilizing agent may comprise a homo- or co-polymer of ethylene or maleic propylene.
- the compatibilizing agent may include polypropylene, which is maleazed and condensed with a monoamined polyamide oligomer.
- the ratio of thicknesses of layers (i) and (ii) and between 25/75 and 65/35 is between 25/75 and 65/35.
- the subject of the invention is also a method of preparation of a film according to the invention, comprising the extrusion of the different layers under the conditions extrusion of polyolefins.
- the polyolefin may be a non-polyolefin functionalized or functionalized polyolefin.
- the polyolefin can also be functionalized at know to be a polymer of alpha-olefins and patterns reagents (the features); such reactive patterns are the functions acids, anhydrides, or epoxy.
- unsaturated epoxides such as (meth) acrylate glycidyl
- carboxylic acids or salts or corresponding esters such as (meth) acrylic acid (this one can be neutralized totally or partly by metals such as Zn, etc.) or by carboxylic acid anhydrides such as maleic anhydride.
- a functionalized polyolefin of a embodiment is for example a PE / EPR mixture, whose weight ratio can vary between wide measures, for example between 40/60 and 90/10, said mixture being co-grafted with an anhydride, in particular anhydride according to a grafting rate of, for example, 0.01 to 5% by weight.
- the acid (meth) acrylic can be salified with Zn or Li.
- alkyl (meth) acrylate refers to the methacrylates and C1-C6 alkyl acrylates, and may be selected from methyl acrylate, acrylate ethyl, n-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.
- polyolefins can also be cross-linked by any suitable process or agent (diepoxy, diacid, peroxide, etc.); the term polyolefin functionalized also includes mixtures of above-mentioned polyolefins with a difunctional reagent such as diacid, dianhydride, diepoxy, etc. susceptible to react with them.
- a difunctional reagent such as diacid, dianhydride, diepoxy, etc. susceptible to react with them.
- copolymers mentioned above can be copolymerized statistically or sequentially and present a linear or branched structure.
- the molecular weight, the MFI index, the density of these polyolefins can also vary to a large extent, this that the man of the art will appreciate.
- Blends of polyolefins, functionalized or otherwise, are also possible. Suitable mixtures are those in which a majority part is composed of unfunctionalized polyolefin and the other part is a functionalized polyolefin, said polyolefin functionalized up to 40% by weight of the mixed.
- the functionalized polyolefin is especially EP / EPR mixture grafted anhydride described above.
- the polyamide / polyolefin alloy having a tension of weak surface can be obtained for example when it is in co-continuous phases.
- This term "alloy" polyamide / polyolefin with co-continuous phases "means the products comprising a polyamide, according to the acceptance classic; a polyolefin, as described above, and when it does not contain enough functionality to ensure compatibility with the polyamide a compatibilizer; polyolefin and polyamide being present in the form of two co-continuous phases, that neither phase is present in dispersed form in the other phase.
- the polyolefin can be functionalized or not, and it can be the mixture of a nonfunctionalized polyolefin and a functionalized polyolefin.
- FIG. 1 is a photomicrograph of a co-continuous phase alloy used in the context of the invention; we note that the phases are interpenetrating (or interpenetrating).
- a polyamide matrix alloy (and polyolefin nodules dispersed in this phase) corresponds to the photomicrograph of FIG.
- the alloy used in the context of the invention will generally have sufficient viscosity to be extruded into film by cast extrusion or extrusion blowing and has, for example, an MFI of 0.5 to 20 (in g / 10 min measured at 235 ° C. under 2.16 kg).
- polyamide is used in its common sense and denotes the condensation products of alpha-omega-amino acids, or the corresponding lactams or one or several substantially stoichiometric combinations one or more aliphatic diamines and / or cycloaliphatic and / or aromatic-aliphatic, or their salts, with one or more dicarboxylic acids aliphatic or aromatic, or mixtures.
- the polyamide is PA6, PA6.6, PA6,10, PA11, PA12, PA6,12, PA12,12 and PA6 / 6.6 (i.e. polyamides obtained from caprolactam, hexamethylenediamine and adipic acid) and PA6 / 12 (caprolactam and lauryllactam).
- the molecular weight of polyamides can vary to a large extent, what the skilled person will appreciate.
- the polyamide / polyolefin ratio in the alloy can vary, what will appreciate the man of the art, the final alloy however, it should preferably not have a phase continuous in which is dispersed another phase.
- the polyamide represents, by weight, from 40 to 65%, advantageously from 50 to 60%, and more particularly from 55 to 60%, the weight of the alloy.
- the compatibilizer is present in a quantity sufficient to ensure compatibility, namely preferably the dispersion one in the other of the two co-continuous phases.
- the compatibilizing agent can represent up to 25% by weight of the final alloy.
- the compatibilizing agent is a product known per se for compatibilizing polyamides and polyolefins, and may be in particular a functionalized polyolefin, such as that described above.
- the alloy polyamide / polyolefin is a PA6 / PP / Agent alloy compatibilizer.
- the compatibilizing agent is preferably based on a homo- or co-polymer of ethylene or propylene.
- the compatibilizing agent is preferably maleicised (by grafting or copolymerization).
- the compatibilizing agent content is for example between 5 and 15% by weight, for example about 10%.
- a preferred alloy is a PA6 / PP / Agent alloy compatibilizer, in which the compatibilizing agent is based on a homo- or co-polymer of ethylene or propylene, which is maléisé and possibly grafted (condensed) by a polyamide oligomer (monoamine).
- the film according to the invention thus has a low surface tension, less than 36 mJ / m 2 , preferably between 31 and 34 mJ / m 2 , ie a low surface tension, and has a low surface tension.
- apolar nature the film according to the invention is therefore substantially of the olefinic type.
- the film according to the invention is therefore substantially non-sticky, and presents at the same time properties fence. It is therefore suitable for uses as diverse as packaging film for example for meat, as sausage skin, SMC film, etc. Moreover, if the films according to the invention some interesting properties of polyolefins they do not exhibit the traditional defects of these. Moreover, the films according to the invention allow the more often to get rid of a layer of binder between the polyolefin layer and the alloy layer, which prevents a film with 5 layers, but without adhesion properties between layers. advantageously in the middle layer is added a product intended for facilitate the adhesion of the layers, without using a diaper of binder. This product may be a grafted polyolefin, a compatibilizing agent as mentioned above.
- additives and adjuvants, as well as other polymers can be added in the different layers of films according to the invention, in quantities that do not affect the desired properties and classics for those skilled in the art.
- additives are anti-UV, anti-oxidants, pigments, fillers such as silica, fibers, etc.
- the thickness of the film according to the invention is conventional, for example between 1 and 500 ⁇ m, typically from 5 to 100 ⁇ m.
- the ratio of the thicknesses of the layers (i) and (ii) can be understood for example between 25/75 and 65/35.
- the film according to the invention may comprise other layers, for example other polymers, between layers (i) and (ii) or outside layers (ii); movies according to the invention may also include other types of film (paper or metal such as aluminum). Movies according to the invention can also be laminated on any substrate appropriate. However, films consisting of a polyolefin core layer between two layers polyamide / polyolefin alloys, used is.
- the films according to the invention can be prepared by any conventional method, in particular by extrusion. (by example on single-screw extruder with mixer profile, twin-screw extruders, sheath extruders, etc.). We can for example use a tri-layer extruder, with temperatures of 210 to 250 ° C for the polyolefin and 240 to 260 ° C for the alloy layer.
- the films are made on a three-layer extruder with a 150mm die, a 0.7mm air gap, a draft speed of 9m / min, a inflation rate of 2.1 for a 500mm flat width; we uses temperatures of 210 to 250 ° C for the polyolefin and 240 to 260 ° C for the alloy layer.
- the invention thus provides olefinic type films but not presenting the traditional defects of polyolefins.
Description
- la figure 1 est une microphotographie d'un alliage à phases co-continues utilisé dans le cadre de l'invention (alliage A des exemples) ;
- la figure 2 est une microphotographie d'un alliage à matrice polyamide.
A titre d'exemple, on peut citer :
- les homopolymères tels que polyéthylène, en particulier LDPE, HDPE, LLDPE ou VLDPE, polyéthylène métallocène ou polypropylène.
- les copolymères éthylène/alpha-oléfine tels que éthylène/propylène, les EPR.
- les copolymères blocs styrène/éthylène-butène/styrène (SEBS), styrène/butadiène/styrène (SBS), styrène/isoprène/styrène (SIS), styrène/éthylène-propylène/styrène (SEPS) et éthylène/propylène/diène (EPDM).
- les copolymères de l'éthylène avec au moins un produit choisi parmi les sels ou les esters d'acides carboxyliques insaturés tel que le (méth)acrylate d'alkyle (par exemple acrylate de méthyle), ou les esters vinyliques d'acides carboxyliques saturés tel que l'acétate de vinyle, la proportion de comonomère pouvant atteindre 40% en poids.
- du PE, du PP, des copolymères de l'éthylène avec propylène, butène, hexène, ou octène contenant par exemple de 35 à 80% en poids d'éthylène;
- des copolymères éthylène et acétate de vinyle (EVA), contenant jusqu'à 40% en poids d'acétate de vinyle;
- des copolymères éthylène et (méth)acrylate d'alkyle, contenant jusqu'à 40% en poids de (méth)acrylate d'alkyle;
- des copolymères éthylène et acétate de vinyle (EVA) et (méth)acrylate d'alkyle, contenant jusqu'à 40% en poids de comonomères;
- les copolymères éthylène/propylène majoritaires en propylène greffés par de l'anhydride maléique puis condensés avec du polyamide (ou un oligomère de polyamide) monoaminé (produits décrits dans EP-A-0342066).
A titre d'exemple de polyoléfines fonctionnalisées de ce dernier type, on peut citer les copolymères suivants, où l'éthylène représente de préférence au moins 60% en poids et où le termonomère représente par exemple de 0,1 à 10% en poids du copolymère :
- les copolymères éthylène/(méth)acrylate d'alkyle ou acide (méth)acrylique/anhydride maléique ou méthacrylate de glycidyle;
- les copolymères éthylène/acétate de vinyle/anhydride maléique ou méthacrylate de glycidyle;
- les copolymères éthylène/acétate de vinyle/(méth)acrylate d'alkyle ou acide (méth)acrylique/anhydride maléique ou méthacrylate de glycidyle.
- le polyéthylène, le polypropylène, les copolymères d'éthylène, tel que éthylène/propylène, éthylène/butène, SEBS, SBS, SIS, SEPS et EPDM, tous ces produits étant greffés par de l'anhydride maléique ou du méthacrylate de glycidyle;
- les copolymères éthylène/(méth)acrylate d'alkyle/anhydride maléique, l'anhydride maléique étant greffé ou copolymérisé;
- les copolymères éthylène/acétate de vinyle/anhydride maléique, l'anhydride maléique étant greffé ou copolymérisé;
- les deux copolymères précédents dans lesquels l'anhydride est remplacé en tout ou partie par du méthacrylate de glycidyle;
- les copolymères éthylène/acide (méth)acrylique, et éventuellement leurs sels;
- les copolymères éthylène/(méth)acrylate d'alkyle/méthacrylate de glycidyle, le méthacrylate de glycidyle étant greffé ou copolymérisé;
- les copolymères greffés constitués d'au moins un oligomère mono-aminé de polyamide et d'un (co)polymère d'alpha-monooléfine greffé par un monomère susceptible de réagir avec la fonction amine dudit oligomère;
- PP maléisé (par ex. à un taux = 0,5%) ;
- SEBS maléisé (par ex. à un taux = 0,5%) ;
- EPR statistique maléisé (par ex. à un taux = 0,5%) ;
- EPDM maléisé (par ex. à un taux = 0,5%) ;
- PP maléisé (par ex. à un taux = 0,5%) greffé (condensé) oligomère de PA, notamment PA6, PA11, PA12 PA6.6/12, de préférence PA6, ledit oligomère étant avantageusement monoaminé (avec un MWn par ex. de Mn=1500) ;
Ex. | Type de polymère | Ratio épaisseurs des couches | Tension de surface (mJ/m2) | Partie apolaire (mJ/m2) | Partie polaire (mJ/m2) |
1 | A | 100 | 32,7 | 32 | 0,7 |
2 | E/B/E | 30/40/30 | 33,6 | 31,5 | 2,1 |
3 | F/C/F | 30/40/30 | 31,6 | 31,5 | 0,1 |
4 | C/G/C | 25/50/25 | 37,2 | 33,9 | 3,3 |
5 | D/G/D | 25/50/25 | 39,3 | 34,5 | 4,8 |
6 | A/G/A | 25/50/25 | 32,1 | 30,9 | 1,2 |
- les exemples 1, 2 et 3 ont une tension de surface faible, de l'ordre de 31-34 mJ/m2 et présentent un caractère quasi apolaire ; ceci est dû aux couches de polyoléfine.
- les exemples 4 et 5 présentent une tension de surface élevée, de l'ordre de 37-39 mJ/m2 et présentent une polarité marquée (de type polyamide).
- l'exemple 6, selon l'invention, présente une tension de surface de l'ordre de 32 mJ/m2, et présente un caractère quasi apolaire ; ce film est donc de type oléfinique.
Claims (14)
- Film comprenant:(i) au moins une couche centrale en polyoléfine; et(ii) au moins deux couches externes en alliage polyamide/polyoléfine présentant une tension de surface inférieure à 36 mJ/m2.
- Film selon la revendication 1, la tension de surface étant comprise entre 31 et 34 mJ/m2 .
- Film selon la revendication 1 ou 2, consistant en une couche centrale en polyoléfine entre deux couches externes en alliage polyamide/polyoléfine.
- Film selon l'une quelconque des revendications 1 à 3, dans lequel la polyoléfine de la couche (i) comprend une polyoléfine fonctionnalisée.
- Film selon l'une quelconque des revendications 1 à 4, dans lequel la polyoléfine de la couche (i) comprend un homo- ou co-polymère d'éthylène ou de propylène.
- Film selon l'une quelconque des revendications 1 à 5, dans lequel la polyoléfine de la couche (i) est un mélange d'une polyoléfine non-fonctionnalisée et d'une polyoléfine fonctionnalisée, ladite polyoléfine fonctionnalisée représentant jusqu'à 40% en poids du mélange.
- Film selon l'une quelconque des revendications 4 à 6, dans lequel la polyoléfine fonctionnalisée est un mélange PE/EPR greffé anhydride maléique.
- Film selon l'une quelconque des revendications 1 à 7, dans lequel l'alliage polyamide/polyoléfine est à phases co-continues.
- Film selon l'une quelconque des revendications 1 à 8, dans lequel l'alliage polyamide/polyoléfine comprend un agent compatibilisant.
- Film selon l'une quelconque des revendications 1 à 9, dans lequel l'alliage polyamide/polyoléfine est un alliage PA6/PP/Agent compatibilisant.
- Film selon la revendication 9 ou 10, dans lequel l'agent compatibilisant comprend un homo- ou co-polymère d'éthylène ou de propylène maléisé.
- Film selon la revendication 9 ou 10, dans lequel l'agent compatibilisant comprend du polypropylène, qui est maléisé et condensé avec un oligomère de polyamide monoaminé.
- Film selon l'une quelconque des revendications 1 à 12, dans lequel le rapport des épaisseurs des couches (i) et (ii) et compris entre 25/75 et 65/35.
- Procédé de préparation d'un film selon l'une quelconque des revendications 1 à 13, comprenant l'extrusion des différentes couches dans les conditions d'extrusion des polyoléfines.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9812247A FR2783747B1 (fr) | 1998-09-30 | 1998-09-30 | Film comprenant une couche centrale en polyolefine et deux couches externes en alliage polyamide/polyolefine |
FR9812247 | 1998-09-30 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0990515A1 EP0990515A1 (fr) | 2000-04-05 |
EP0990515B1 true EP0990515B1 (fr) | 2005-06-01 |
Family
ID=9531040
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99402330A Expired - Lifetime EP0990515B1 (fr) | 1998-09-30 | 1999-09-23 | Film comprenant une couche centrale en polyoléfine et deux couches externes en alliage polyamide/polyoléfine |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0990515B1 (fr) |
JP (1) | JP2000108263A (fr) |
KR (1) | KR20000023555A (fr) |
CN (1) | CN1254643A (fr) |
AT (1) | ATE296727T1 (fr) |
CA (1) | CA2282934A1 (fr) |
DE (1) | DE69925554T2 (fr) |
ES (1) | ES2244161T3 (fr) |
FR (1) | FR2783747B1 (fr) |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4660894B2 (ja) * | 1999-12-14 | 2011-03-30 | 東レ株式会社 | 気体および/または液体バリア部品用樹脂成形体およびそれからなる薬液またはガス搬送および/または貯蔵用容器およびその付属部品 |
EP1156080A1 (fr) * | 2000-05-15 | 2001-11-21 | Atofina | Feuille multicouche coextrudée comprenant deux couches extérieures en polyamide ou alliage polyamide/polyoléfine et couche centrale en polyoléfine ou polyamide ou alliage polyamide/polyoléfine |
US6555213B1 (en) * | 2000-06-09 | 2003-04-29 | 3M Innovative Properties Company | Polypropylene card construction |
KR100508907B1 (ko) | 2001-12-27 | 2005-08-17 | 주식회사 엘지화학 | 차단성이 우수한 나노복합체 블렌드 조성물 |
FR2844517B1 (fr) * | 2002-09-16 | 2004-10-15 | Atofina | Liant de coextrusion a base de polyethylene metallocene et lldpe cogreffes, de sbs et de pe |
US7029735B2 (en) | 2003-03-17 | 2006-04-18 | Arkema | Polyamide and polyolefin blends with a polyamide matrix and containing nanofillers |
CN100523086C (zh) * | 2003-03-17 | 2009-08-05 | 阿托菲纳公司 | 以聚酰胺为基体并且含有纳米填料的聚酰胺和聚烯烃共混物 |
DE102008056349A1 (de) * | 2008-11-07 | 2010-05-12 | Lanxess Deutschland Gmbh | Folien mit erhöhter Beständigkeit gegenüber Styrol |
FR2969532B1 (fr) * | 2010-12-23 | 2013-06-28 | Arkema France | Encapsulant d'un module photovoltaïque |
FR2971626B1 (fr) * | 2011-02-11 | 2015-12-04 | Arkema France | Film bi-couches d'un module photovoltaique |
JP5798595B2 (ja) * | 2012-06-22 | 2015-10-21 | 株式会社豊田中央研究所 | 樹脂組成物 |
CN108291060B (zh) | 2015-12-01 | 2021-04-16 | 丰田纺织株式会社 | 成型体和其制造方法 |
KR102021019B1 (ko) | 2015-12-01 | 2019-09-11 | 도요다 보쇼꾸 가부시키가이샤 | 개질제 및 그 사용 방법, 개질제의 제조 방법 및 첨가재용 담체 |
JP6288142B2 (ja) | 2016-03-31 | 2018-03-07 | トヨタ紡織株式会社 | 分散径の調整方法及び熱可塑性樹脂組成物 |
BR112019001710B8 (pt) * | 2016-07-28 | 2022-09-06 | Advansix Resins & Chemicals Llc | Método para formar um filme soprado, filme soprado, e copolímero de poliamida |
BE1024995B1 (nl) * | 2017-07-25 | 2018-09-13 | Sb Diest Nv | Verbeterde meerlagige plastic film en werkwijze voor het fabriceren ervan |
JP7234597B2 (ja) * | 2018-11-19 | 2023-03-08 | 凸版印刷株式会社 | 包装材用積層フィルム、包装材、及び包装体 |
EP3722085A1 (fr) * | 2019-04-12 | 2020-10-14 | Nitto Denko Corporation | Films multicouches pour des applications d'airbag et procédés associés |
EP3722086A1 (fr) | 2019-04-12 | 2020-10-14 | Nitto Denko Corporation | Films multicouches pour des applications d'airbag |
JP7409045B2 (ja) | 2019-11-25 | 2024-01-09 | Toppanホールディングス株式会社 | 包装材用シーラントフィルム、これを用いた包装材及び包装体 |
CN116218208B (zh) * | 2023-04-24 | 2024-03-19 | 上海金发科技发展有限公司 | 一种pa/pp合金材料及其制备方法和应用 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69212681T2 (de) * | 1991-03-29 | 1997-01-02 | Atochem Elf Sa | Trennfolie aus Polyamid/Polyolefin-Mischungen für formbaren Schichtwerkstoff und damit hergestellter Schichtwerkstoff |
US5601770A (en) * | 1995-09-29 | 1997-02-11 | Airtech International, Inc. | Method for producing sheet molding compounds utilizing a multilayered, multistructured, multipolymer release / barrier film |
FR2743746B1 (fr) * | 1996-01-23 | 1998-04-03 | Atochem Elf Sa | Nouveau film de relachement pour produit de compoundage de moulage de feuilles |
US20030129428A1 (en) * | 1996-06-10 | 2003-07-10 | Mingliang Lawrence Tsai | Multilayer polyamide film structures |
-
1998
- 1998-09-30 FR FR9812247A patent/FR2783747B1/fr not_active Expired - Fee Related
-
1999
- 1999-09-23 ES ES99402330T patent/ES2244161T3/es not_active Expired - Lifetime
- 1999-09-23 EP EP99402330A patent/EP0990515B1/fr not_active Expired - Lifetime
- 1999-09-23 AT AT99402330T patent/ATE296727T1/de not_active IP Right Cessation
- 1999-09-23 DE DE69925554T patent/DE69925554T2/de not_active Expired - Lifetime
- 1999-09-27 CA CA002282934A patent/CA2282934A1/fr not_active Abandoned
- 1999-09-29 CN CN99123910A patent/CN1254643A/zh active Pending
- 1999-09-30 JP JP11315772A patent/JP2000108263A/ja not_active Withdrawn
- 1999-09-30 KR KR1019990042018A patent/KR20000023555A/ko not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
DE69925554T2 (de) | 2006-02-02 |
JP2000108263A (ja) | 2000-04-18 |
DE69925554D1 (de) | 2005-07-07 |
CA2282934A1 (fr) | 2000-03-30 |
CN1254643A (zh) | 2000-05-31 |
EP0990515A1 (fr) | 2000-04-05 |
FR2783747A1 (fr) | 2000-03-31 |
ATE296727T1 (de) | 2005-06-15 |
FR2783747B1 (fr) | 2000-12-08 |
ES2244161T3 (es) | 2005-12-01 |
KR20000023555A (ko) | 2000-04-25 |
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